4, 4&#39;-bis (1, 1, 3, 3-tetrafluoro-1, 3-dichloro-2-hydroxy-2-propyl)-diphenylether



tained.

, by Weight. I

United States Patent This invention relates to certain derivatives offluorinated ketones useful as active insecticidal and miticidaltoxicants.

These derivatives of fiuorinated ketones are:

4- hexafluoro-2-hydroxy-2-propyl) -diphenylmethane, 4- hexafiuoro-Z-hydroxy-Z-propyl) -diphenylether, 4,4-bis (hexafluoro-Z-hydroxy-Z-propyl)-diphenylether,

. 4,4'-bis (hexafluoro-Z-hydroxy-Z-propyl) diphenylsulfide,

4,4'-bis hexafluoro-2-hydroxy-2-propyl) -biphenyl,

4,4"-bis hex afioro-Z-hydroxy-Z-propyl) -p-terphenyl,

4- hexafluoro-Z-hydroxy-Z-propyl) dodecyl-b enzene,

4,4'-bis( l 1,3,3-tetrafluoro-1,3-dichloro-2-hydroxy- 2-propyl)-diphenylether and mixtures thereof. Except for 4-(hexafluoro 2-hydroxy2-propyl-diphenylether and 4,4'bis(hexafiuoro-2- hydroxy2-propyl)-diphenylether, the fluorinated ketone derivatives arecompounds not heretofore known in the .11.

The 'fluon'n'ated ketone derivatives may be prepared in high yield byintimately admixing the appropriate ketones and aromatic compounds inthe presence of aluminum chloride as catalyst. The ketone reactantsemployed are -hexafiuoroacetone or sym-tetrafluorodichloroacetone, andthe aromatic compound reactants employed are diphenylmethane,diphenylether, diphenylsulfide, biphenyl, p-terphenyl or dodecylbenzene.

'Thealuminum chloride is generally employed in ratio 1 of at least about0.05 mol per mol of ketone reactant.

Although smaller amounts of aluminum chloride may be employed,substantially lower product yields are obtained.

-If required, the aluminum chloride may be employed in ratio as high asabout 1.1 mols per mol of ketone reactant.

, Depending on whether a 1:1 molar product or 2:1 molar product isdesired, the ketone and aromatic compound are reactedin-rnol ratio ofaboutl or about 2 mols of ketone per mol of aromatic compound. Incertain cases, a mixture of 1:1 molar and 2:1 molar products is ob- Whenthe aromatic compound is a liquid, the use of a solvent is optionalsince the aromatic compound itself' 1 functions as a solvent. When,however, the aromatic com I pound itself functions as a solvent. When,however, the

aromatic compound is a solid, a solvent is required. Suitable solventsinclude carbondisulfide, aliphatic hydrocarbons such as heptane, hexane,etc., fluorochloro-substituted aliphatic hydrocarbons such astrifluorotrichloroethane and chlorinated aliphatic hydrocarbons such astetrachloroethylene- Reaction temperatures range from about -20 to C.The reaction is generally carried out at these temperatunes for areaction period of about% hour or higher, depending on the quantity ofproduct being prepared.

The following examples illustrate preparation of the fiuorinated ketonederivatives. In the examples, parts are Example 1 A solution of 33.6parts of diphenylmethane and 1 part of aluminum chloride in about 253parts of carbon disulfide was introduced into a reaction vessel and thentreated at room temperature with a stream of hexafluoroacetone such thatthe hexafluoroacetone refluxed genfly in a dryice condenser placed inthe neck of the reaction vessel. When about the theoretical amount ofhexafluoroacetone required for a 1:1 molar product had been added, themixture formed two layers. The organic layer was separated, washed withwater and then taken up in warm aqueous 10% sodium hydroxide. Theresultant sodium hydroxide layer was washed with carbon tetrachloride.Two parts of charcoal were then added, and the solution was boiled for 5minutes, filtered and acidified. An oil was obtained which was washedwith water and heated to 250 C. to drive oli volatile material. It wasthen taken up in hexane, stirred with parts of activated alumina for 1hour, filtered and the solvent removed. The residue was heated to C. todrive all residual solvent.

The product comprising 4-(hexafluoro 2-hydroxy-2-propyl)-diphenylmethane was distilled off at 188-190 C. at 16 mm. Hg andconstituted 49 parts (73% yield). The product may be represented by thefollowing structural formula:

Fluorine analysis of the product was 37.0%, demonstrating thattheproduct was predominantly 1:1 molar product.

- Example 2 34 parts of diphenylether were dissolved in about 127 partsof carbon disulfide, and 1 part of aluminum chloride was added to thesolution. The solution was then treated with hexafluoroacetone until nofurther absorption of the ketone occurred. The reaction temperature wasmaintained below 30 C. Absorption of hexafluoroacetone became slow after20'parts had been added, necessitating the addition of--'0.5 partofaluminum chloride to accelerate the reaction. The reaction product wasworked up as in Example 1 to give 44 parts (65% yield) of productboiling at 183 C. at 15 mm. Hg.

Fluorine analysis of" the product was 40.0%, showing that the productwas a mixture of 4-(hexafluoro-2-hydroxy 2-propyl)-diphenylether and4,4'-bis(hexafluor'o- 2-hydroxy 2'-propyl)-diphenylether. The structuralformulae for these compounds are set forth below;

QQCwHXCFn 1 :1 molar product 2 :1 molar product j E ile. v

17 parts of diphenylether and2 parts of aluminum chloride were stirredand-treated with a stream of hexafluoroacetone as rapidly as absorptionoccurred. The temperature of the reaction mixture rose to about 46 C.during the course of the addition and dropped to 35 C. in the latterpart of the reaction. 36 parts of hexafluo'roacetone were absorbed. Thereaction 'mixture was decomposed with 100 parts of cold water, and theresultant organic layer was taken up in carbon tetrachloride, washedwith water, dried and distilled. There were obtained 28 parts of4,4'-bis(hexafluoro 2-hydroxy-2-propyl)-diphenylether boiling at C. at 3mm. Hg. Fluorine analysis of the product was 44.6% (theoretical 45.4%)and hydrogen analysis was 1.90, 1.71% (theoretical 1.99%).

3 Example 4 A solution of 37.2 parts of diphenylsulfide and 1 part ofaluminum chloride in about 505 parts of carbon disulfide was treatedwith hexafluoroacetone with external cooling so that a temperature--f-03 C. was maintained. 69 parts of hexafluoroacetone were used overaperiod of 2-hours. The reaction mixture was decomposed with 100 partsof water. The'carbon disulfide was distilled off, and the organicresidue was taken up in chloroform, washed, dried and distilled. 90parts(87% yield) of 4,4-bis(hexafiuoroZ-hydroxy-Z propyl) diphenylsulfideboiling at 140-151 C. at about :1 mm. Hg were obtained. The product maybe represented by the following structural formula:

ccrnir )c-QsG-cwmwmu Sulfur analysis of the product gave 6.0%, as compared to a theoretical value of 6.2%.

Example 5 A solution of 32 parts of a 1:1 molar product of biphenyl andhexafiuoroacetone .(prepared by the general procedure of Example 1 inabout 253 .parts of carbon disulfide was admixed with 1 part of aluminumchloride and treated with hexafiuoroacetone as rapidly as completeabsorption occurred. Increments of 1 part of aluminum chloride wereadded when the rate of reaction dropped considerably. A total of 13.5parts of aluminum chloride was added. An induction period of aboutminutes was observed, after which reaction temperature rose to 36 C.and-remained there until all of the hexafiuoroacetone had been absorbed.Decomposition of the reaction mixture with 200 parts of water yielded asolid which was filtered off. The solid was taken up in aqueous sodiumhydroxide, decolorized with charcoal and acidified. The product obtainedwas crystall'zed from alcohol-water twice to give 34 parts (70% yield)of 4,4-bis(hexafluoro-Z-hydroxy- 2-propyl)-bipheuyl melting at125..8126.4' C. The prodnot is represented by the following structuralformula:

rornirornrou (oral Example 6 A suspension of 46 parts of gp-terphenyl inabout 1263 parts of carbon disu-lfide was treated in the presence 'of 2parts of aluminum chloride with hexafluoroacetone so that absorption ofthe hexafiuoroacetone was complete. Additional aluminum chloride wasintroduced as needed when the reaction rate dropped. A total of 88 partsof hexafluoroacetone and T1 parts of aluminum chloride was used.Decomposition of the reaction mixture with 200 parts of water yielded 95parts (86% yield) of a powder melting at 175 C I Analysis of the productgave 35.2% fluorine, showing that the product was a mixture.o-f4-(hexafiuoro-2-hydroxy-2-propyl)-p-terphenyl and4,4"-bis(hexafluoro-2- hydroxy-Z-propyl)-p-terphenyl. The structuralformulae for these compounds are given below:

1:1 molar product 2 :1 molar product Example 7 propyl)-dodecylbenzeneboiling at 128l30 C. at 2 mm. Hg were obtained. The product isrepresented by the following structural formula:

Fluorine analysis of the product was 27.7% andhydrogen analysis was7.58%, as compared to the theoretical values of 27.7% and 7.52%,respectively.

Example 8 A m xture of 34 parts of diphenylether and parts tionated.46.2 parts (62% yield) of 4,4'-'bis(1,1,'3-tetrafluoro 1,3dichloro-2-hydroxy-2-propyl)-diphenylether boiling mostly at 200-202 C.at 2 mm. Hg were'obtained.

The product is represented bythe following structural formula:

Fluorine analysis of the product was 25.7% and hydrogen analysis was1.84%. Theoretical values for the fluorine D and hydrogen are 26.8% and1.76%, respectively.

As indicated above, the fiuorinated ketone derivatives of this inventionfind valuable application as active insecticidal andmiticidaltoxicant-s. The compou-ndscan-be employedeither as soletoxic'ant ingredients or they can be emlpoyed in conjunction with otherpesticidally active materials such as DDT, benzene hexachloride, etc.

The compounds are ordinarily applied as toxicants for combat'ting insectand mite pests in c'oniunct-ionwith a carrier which may be an inertsolid, liquid or gaseous material, or a bait.

When employed in the form of a powder, fine orgranular dust for killinginsects and mites, the toxicant may be mixed with a substantialproportionof'anysutiable inert material or diluent such as known gradesof prepared parasiticide carrier clays, pyrophyllite, fullers earth,bentonite, sulfur, lime, talc, whiting, diatomac'eousearth-etc. Suitabledusts of this type usually contain not less than 0.5%, and preferablynot less than 1% of toxicant.

Liquid insecticide or miticide sprays containing the toxicant may beprepared by first forming a solution of the compound in a suitableorganic solvent e.g., xylene, toluene or benzene, and preferably addinga small-amount of emulsifying agent commonly employed in the-art, suchas diglycol oleate or p-isooctyl phenyl ether of polyethylene glycol.The resulting concentrate solution is incorporated with water in amountssufficient to form an aqueous spray dispersion or emulsion having thedesired active ingredient concentration. In a preferred embodiment,aqueous. spray dispersions or suspensions may be formed by incorporatingin water so-called dry wettable spray powders or water-dispersiblepastes containing-the fluori nated ketone derivatives. These mixturesmay also include inert diluents, suitable quantities of wetting,dispersing and suspending agents and, if desired, secondary toxicants. T

The aqueous spray dispersions of this invention should preferablycontain the toxicant in amount not less than /s pound per 106 gallons ofspray, the more usual amount being in the range of /2 to 2 pounds pergallons of spray.

Bait preparations of the invention should contain the toxicant inassociation with a substance attractive to the pest, such as a food orbreeding material. Usually, /2 to 1% by weight of the toxicant would beused in the bait.

The following table shows the results of tests on application of thefiuorinated ketone derivatives to insects and mites. The tests werecarried out using 2 pounds of toxicant per 100 gallons of 50:50acetone-water.

them with the formulation. Following treatment, the pea aphids wereconfined to untreated broad bean plants. Record of kill was made threedays after treatment.

The tests on toxicity to Mexican bean beetle larvae (Epilachnavarivestis) and to southern armyworm larvae (Prodenia eridania) were runby spraying horticultural (cranberry) bean plants with the formulationand allowing the plants to dry. The larvae were confined to the MexicanBean Pea Aphids, Southern Two-Spotted Compound Beetle Larvae, PercentKill Armyworm Mites,

Percent Kill Larvae, Percent Kill Percent Kill4-(hexafluoro-2-hydroxy2-propyl) -diphenylmethane 100 100 A mixture of4'(hexafluoro-2-hydroxy-2-propyl)-diphenylether and 4,4-bis (hexafluoro-Z-hydxoxy-Z-propyl)-dipheny1ether- 4,4-his (hexafluoro-2-hydroxy-2propyl) -diphenyl ether4,4'-bis(hexafiuoro-Zhydroxy-Q-propyl-diphenylsulfide4,4-bis(hexafiuoro-2hydroxy-Z-propyl) -bipheny1 A mixture of4-(hexailuoroQ-hydroxyQ-propyl)-p-terphenyl and 4-4-his (hexafluoro-Z-hydroxy-Z-propyl)-p'terphenyl4-(hexafiuoro-Z-hyclroxy-Z-propyl) dodeeylbenzene 4,4-bis (1,,3,3-tetrafluoro-1 ,3-diehloro-2-hydroxy-2-prop yl)- (liphenylether Thefollowing results were obtained in tests on houseflies using 1.0% of thetoxicant in dry food (sugar):

The tests on toxicity to mites were carried out on twospotted mites (Tetranychus telarius) by spraying the formulation onto horticultural(cranberry) bean plants infested with the mites. Following treatment,the plants were stored on racks in irrigated trays under greenhouseconditions. Mortality counts were made three days after treatment.

The tests on toxicity to pea aphids (Macrosiphum pisi) were run byremoving the pea aphids from infested broad bean plants, placing them ona wire screen and spraying treated foliage by means of wire cages.Record of kill was made three days after treatment.

The tests on toxicity to honseflies (Musca domestica) were run bytreating dry food (sugar) with the toxicant, allowing the food to dryand then repulverizing the food. The treated food was placed inemergence cages containing pupae, and percent kill was noted seven andnine days after treatment.

While we have described the preferred embodiments for carrying out ourinvention, it will be apparent that many changes may be made withoutdeparting from the spirit of the invention.

We claim:

4.4 bis(1,1,3,3 tetrafluoro-1,3-dichloro-2-hydroxy-2- propyl)-diphenylether.

References Cited UNITED STATES PATENTS 3,236,894 2/1966 England 260-574BERNARD HELFIN, Primary Examiner. CHARLES B. PARKER, L. ZITVER,Examiners. D. R. PHILLIPS, Assistant Examiner.

